Cyclohexane derivatives

ABSTRACT

Various substituted cyclohexane-1,3-diones are useful as herbicides.

This is a continuation of application Ser. No. 620,862 filed Oct. 9, 1975, now U.S. Pat. No. 4,011,256, which in turn is a divisional application of application Ser. No. 490,349 filed July 22, 1974, now U.S. Pat. No. 3,950,420.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to novel compounds of cyclohexane derivatives, to a process for the preparation thereof and their uses as selective herbicide.

In particularly this invention relates to new herbicidally active compositions and to method for killing undesired plants.

It has been found that outstanding herbicidal activity can be obtained by applying to the weed habitat, the compounds represented by the following formula: ##STR1## wherein R₁ is selected from the group consisting of hydrogen, alkyl and phenyl,

R₂ is selected from the group consisting of alkyl, straight or branched chain lower alkenyl, lower alkynyl, lower alkoxyalkyl, lower alkylthiomethyl, lower alkoxycarboxyl and benzyl,

X is a same or different substituent which is selected from the group consisting of alkyl, lower alkoxycarbonyl, halogen, cyano, phenyl, phenyl substituted with halogen or methoxy, styryl, furyl, thienyl, 5,5-pentamethylene and 4,5-tetramethylene,

n is 0 or an integer from 1 to 6;

Or a hydrate or a metal salt of the compound defined herein above.

Preferred are those compounds represented by the following formula: ##STR2## wherein R₁ is ethyl or propyl group and R₂ is ethyl, propyl, allyl or propargyl group.

Particularly preferred because of their high order of herbicidal activity are:

2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione

2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione

2-[1-(propargyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione

2-[1-(ethoxyamino)propylidene]-5-isopropylcyclohexane-1,3-dione

2-[1-(allyloxyamino)propylidene]-5-isopropylcyclohexane-1,3-dione

It is expected that the said compound represented by the above formula [I] has the following three chemical formulae because of tautomerism:

An explanation of the drawing:

FIG. 1 is the infrared spectrum of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione

FIG. 2 is the infrared spectrum of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione hydrate

FIG. 3 is the infrared spectrum of 2-[1-(allyloxyamino)butylidene]-5,5-dimethyl cyclohexane-1,3-dione

FIG. 4 is the infrared spectrum of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione hydrate

The compounds of this invention can be prepared in accordance with the following equation: ##STR4## wherein R₁, R₂, X and n are as previously defined.

The above reaction can be conducted in an inert solvent.

As an inert solvent, acetone, ether, methylalcohol, ethylalcohol, isopropylalcohol, benzene, tetrahydrofuran, chloroform, acetonitrile, dichloroethane, dichloromethane, ethyl acetate, dioxane, toluene, xylene and dimethyl sulfoxide etc. are used.

Reaction temperature is from -10° C to the boiling point of employed solvent, preferably from 10 to 60 and the reaction terminates between 0.5 and several hours.

After the reaction terminated, the employed solvent, if necessary, is replaced and then, the reaction mixture is extracted with an alkaline solution and further, an alkaline layer is acidified with hydrochloric acid, whereby the crude product is isolated from the reaction mixture by extraction with solvent or by filtration.

In case of crystalline substance, the crude product can be purified by recrystallization and in oily substance the crude product can be purified by distillation or isolation by column chromatography.

A chemical formula for the resulting purified compound can be confirmatively identified by means of an elementary analysis, NMR spectrum and IR spectrum.

When above formula [VI] represents 5,5-dimethyl-2-acyl-3-hydroxy-2-cyclohexene-1-one, above starting compound can be prepared in accordance with the following equation: ##STR5## wherein R₁ is as previously defined.

It is also expected that the starting compound represented by the formula [VI] has the same three chemical formulas as the formula [I] because of tautomerism.

The sodium and potassium salts are prepared by treating a compound of formula [I] above with a sodium or potassium hydroxide in aqueous solution or an organic solvent such as acetone, methanol ethanol or dimethylformamide. The salts are isolated by filtration or by evaporation of the resulting solution.

The calcium, barium, manganese, copper, zinc, nickel, cobalt, iron and silver salts are prepared from the sodium salt by treatment with the appropriate inorganic metal salt, e.g. calcium chloride, barium chloride, copper sulfate, zinc chloride, nickel chloride, and cobalt nitrate.

The calcium salt is also prepared by treating a compound of formula [I] above with calcium hydroxide.

Some metal salt of the present invention produced with above mentioned process may cause partially a chemical change or a decomposition at a high temperature, so that it does not show a clear melting point. Therefore, by applying infrared ray absorptive spectrum to the raw material and the reaction compound, a formation of the metal salt can be identified through a transference of absorption band and a change of absorption intensity. In the other words, the raw material compound having the said general formula [I] indicates an absorption of carbonyl group at a wavelength 1605cm⁻¹ and 1655cm⁻¹, whereas the corresponding metal salt shows the absorption at a side of longer wavelength. Further, in some occasion, an anion such as OH⁻ may be simultaneous coordinated with a metal atom of some metal salt obtained above.

Some of the compound of this invention may form hydrate thereof as follows: ##STR6## wherein R₁, R₂, X and n are as previously defined.

The hydrate of the compound of the invention also has superior herbicidal activity.

In order to facilitate a clear understanding of the invention, the following preferred specific embodiments are described as illustrative and not as limiting the invention.

Example 1. Preparation of 2-[1-(ethoxyamino)ethylidene]-5,5-dimethylcyclohexane-1,3-dione

1.8g (0.01 mol) of 2-acetyl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one was dissolved in 10ml of ethanol and 0.6g (0.01 mol) of ethoxyamine was added to it and the resulting solution was stirred at a room tempereture during 3 hours and then, the said ethanol was distilled off from it under a reduced pressure and a residual material was dissolved in chloroform.

The resulting chloroform solution was extracted for two times with aqueous solution containing 5 weight percent of sodium hydroxide and an alkaline layer produced thereto was acidified with hydrochloric acid and then an oily material separated thereto was extracted for two times with 10ml of chloroform.

A chloroform layer produced thereto was washed with water and it was dried and then, it was distilled off under a reduced pressure and thereby, the objective compound, as a colorless, oily material was obtained.

A yield amount : 2.1g (93 weight percent of yield rate)

A refractive index: n_(D) ²¹.5 1.5094

Example 2.

The following compounds (C) can be synthesized by the method of Example 1 substituting the appropriate substituted 2-acyl-3-hydroxy-2-cyclohexene-1-one (A) for 2-acetyl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one and the appropriate 0-substituted hydroxyamine (B) for ethoxyamine.

Compound No. 31

(A) 5,5-Dimethyl-3-hydroxy-2-propyonyl-2-cyclohexene-1-one, 1.96g

(B) Ethoxyamine, 0.67g

(C) 2-[1-(Ethoxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 2.3g (97 weight percent of yield rate)

refractive index: n_(D) ²⁴ 1.5027

Compound No. 50

(A) 5,5-Dimethyl-3-hydroxy-2-propyonyl-2-cyclohexene-1-one, 3.92g

(B) Allyloxyamine, 1.6g

(C) 2-[1-(Allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 4.6g (92 weight percent of yield rate)

refractive index: n_(D) ²⁴ 1.5119

Compound No. 75

(A) 2-Butyryl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one, 2.1g

(B) Ethoxyamine, 0.67g

(C) 2-[1-(Ethoxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 2.1g (83 weight percent of yield rate)

refractive index: n_(D) ²¹ 1.4965

Compound No. 83

(A) 2-Butyryl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one, 2.1g

(B) Allyloxyamine, 0.8g

(C) 2-[1-Allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 2.2g (83 weight percent of yield rate)

refractive index: n_(D) ²¹ 1.5089

Compound No. 96

(A) 2-Butyryl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one, 2.1g

(B) Hexyloxyamine, 1.29g

(C) 2-[1-(Hexyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione,

yield amount: 2.5g (81 weight percent of yield rate)

refractive index: n_(D) ²⁵ 1.4725

Example 3. 2-[1-(allyloxyamino)ethylidene]-5,5-dimethylcyclohexane-1,3-dione

1.8g (0.01 mol) of 2-acetyl-5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one was dissolved in 10ml of ethanol and then, 0.73g (0.01 mol) of allyloxyamine was added in it and the resulting solution was agitated at 50° C during one hour and then, the said ethanol was distilled off under a reduced pressure and a residual material was dissolved in chloroform.

The resulting chloroform solution was extracted for two times with 7ml of an aqueous solution containing 10 weight percent of caustic soda. An alkaline layer produced thereto was acidified with hydrochloric acid and a separated crystal was filtered and washed with water and then, it was dried. Then, the said crystal was recrystallized from n-hexane and thereby, the objective compound was obtained as a colorless crystal.

A yield amount: 2.2g (93 weight percent of yield rate)

A melgint point: 30.5 to 31.5° C

Example 4. Cobalt salt of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione

Two gram of 2-[1-allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione were dissolved in 10ml of acetone, and to which 20ml of water containing 0.32g of sodium hydroxide were added. After stirring 10 minutes, 5ml of water containing 1.16g of cobalt nitrate [CO(NO₃)₂ ·6H₂ O] were added dropwise to the mixture. After stirring well, the precipitate was filtrated, washed with water and ether and dried. Gray crystal having a decomposition point of 153°-154° C was obtained. Yield amount: 2.2g (98 weight percent of yield rate).

Example 5.

The following compounds (C) can be synthesized by the method of Example 4 substituting the appropriate substituted cyclohexane-1,3-dione (A) for 2-[1-(allyloxyamino)propylidene]5,5-dimethylcyclohexane-1,3-dione, the appropriate inorganic metal salt (B) for cobalt nitrate, and the appropriate amount of sodium hydroxide (D).

Compound No. 141

(A) 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (2.1g)

(B) Nickel chloride NiCl₂ ·6H₂ O (0.95g)

(C) Nickel salt of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (2.2g), 94 weight percent of yield rate, decomposition point: over 250° C

(d) sodium hydroxide (0.32g)

Compound No. 150

(A) 2-[1-(benzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (3.1g)

(B) Copper sulfate CuSO₄ ·5H₂ O (1.25g)

(C) Copper salt of 2-[1-(benzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (3.2g), 93 weight percent of yield rate, decomposition point: 126°-127° C

(d) sodium hydroxide (0.4g)

Compound No. 112

(A) 2-[1-(allyloxyamino)ethylidene]-5-phenylcyclohexane-1,3-dione (2.8g)

(B) Copper sulfate CuSO₄ ·5H₂ O (0.125g)

(C) Copper salt of 2-[1-(allyloxyamino)ethylidene]-5-phenylcyclohexane-1,3-dione (3g), 95 weight percent of yield rate, decomposition point: 188°-189° C

(d) sodium hydroxide (0.4g)

Example 6. Sodium salt of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione

2.6g of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione was dissolved in 20ml of acetone. 0.4g of sodium hydroxide dissolved in 5ml of water was added to the solution. The solvent was evaporated at reduced pressure after stirring 10 minutes. White crystal having a melting point of 80° to 82° C was obtained by crystallizing the glass-state substance from the mixture of ethanol and benzene.

Yield amount: 2.6g (91 weight percent of yield rate)

Example 7. Calcium salt of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione

2.5g of 2-[1-(allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione was dissolved in 20ml of ethanol. 0.37g of calcium hydroxide dissolved in 20ml of water was added little by little to the solution under stirring. After stirring 1 hr. the insoluble substance was filtrated. The filtrate was evaporated at reduced pressure and precipitated white crystal was washed and dried.

Yield amount; 2.7g (100 weight percent of yield rate)

Decomposition point; 107°-108° C

Example 8. 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione hydrate

2.65g of 2-[1-(allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione was added to 10ml of water and the mixture was vigorously stirred. After several minutes, the precipitate was filtered, washed with water and dried. White crystal having a melting point of 46°-47° C was obtained.

Yield amount: 2.8g (100 weight percent of yield rate)

Example 9

The following hydrate compounds (B) can be obtained by the method of Example 8 substituting the appropriate substituted cyclohexane-1,3-dione (A) for 2-[1-(allyloxyamino)-butylidene]-5,5-dimethylcyclohexane-1,3-dione.

Compound No. 154

(A) 2-[1-allyloxyamino)propylidene]-5-methylcyclohexane-1,3-dione (2.37g)

(B) 2-[1-(allyloxyamino)propylidene]-5-methylcyclohexane-1,3-dione hydrate (2.5g)

Yield rate: 100 weight percent, m.p. : 46°-48° C

Compound No. 156

(A) 2-[1-(ethoxyamino)propylidene]-5-phenylcyclohexane-1,3-dione (2.87g)

(B) 2-[1-(ethoxyamino)propylidene]-5-phenylcyclohexane-1,3-dione hydrate (3.0g)

Yield rate: 100 weight percent, m.p. : 67°-68° C

In addition to the above mentioned compounds described in the preceding example, some typical compounds of the present invention are listed in Table 1.

                                      Table 1                                      __________________________________________________________________________     Compd. No.                                                                             Chemical Name          Physical Constant                               __________________________________________________________________________     1       2-[1-(allyloxyamino)methylidene]-5,5-                                          dimethylcyclohexane-1,3-dione                                                                         m.p. 55-60° C                            2       2-[1-(ethoxyamino)ethylidene]-cyclo-                                           hexane-1,3-dione       m.p. 48-50° C                            3       2-[1-(ethoxyamino)ethylidene]-4-cyano-                                         5,5-dimethylcyclohexane-1,3-dione                                                                     n.sub.D.sup.23.5 1.5280                         4       2-[1-(ethoxyamino)ethylidene]-4-iso-                                           propylcyclohexane-1,3-dione                                                                           n.sub.D.sup.24 1.5115                           5       2-[1-(ethoxyamino)ethylidene]-4-                                                                      n.sub.D.sup.22.5 1.5047                                 ethoxycarbonyl-4-ethylcyclohexane-                                             1,3 dione                                                              6       2-[1-(ethoxyamino)ethylidene]-4-bromo-                                                                n.sub.D.sup.23 1.5405                                   5,5-dimethylcyclohexane-1,3-dione                                      7       2-[1-(ethoxyamino)ethylidene]-4-                                                                      n.sub.D.sup.21 1.5050                                   ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                       8       2-[1-(ethoxyamino)ethylidene]-5-                                                                      n.sub.D.sup.24 1.5132                                   ethylcyclohexane-1,3-dione                                             9       2-[1-(ethoxyamino)ethylidene]-4-                                                                      n.sub.D.sup.25 1.5065                                   methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                       10      2-[1-(ethoxyamino)ethylidene]-5,5-                                                                    n.sub.D.sup.21.5 1.5094                                 dimethylcyclohexane-1,3-dione                                          11      2-[1-(ethoxyamino)ethylidene]-5-                                                                      m.p. 56-57° C                                    phenylcyclohexane-1,3-dione                                            12      2-[1-(allyloxyamino)ethylidene]-                                                                      m.p. 55-57° C                                    cyclohexane-1,3-dione                                                  13      2-[1-(allyloxyamino)ethylidene]-4-                                                                    n.sub.D.sup.31 1.5468                                   bromo-5,5-dimethylcyclohexane-1,3-                                             dione                                                                  14      2-[1-(allyloxyamino)ethylidene]-4-                                                                    m.p. 78-80° C                                    cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                  15      2-[1-(allyloxyamino)ethylidene]-4-                                                                    n.sub.D.sup.21 1.5128                                   ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                       16      2-[1-(allyloxyamino)ethylidene]-4-                                                                    n.sub.D.sup.21 1.5095                                   methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                       17      2-[1-(allyloxyamino)ethylidene]-5-                                                                    n.sub.D.sup.26 1.5203                                   ethylcyclohexane-1,3-dione                                             18      2-[1-(allyloxyamino)ethylidene]-5,5-                                                                  m.p. 30.5-31.5° C                                dimethylcyclohexane-1,3-dione                                          19      2-[1-(allyloxyamino)ethylidene]-5-                                                                    m.p. 34-35° C                                    phenylcyclohexane-1,3-dione                                            20      2-[1-(propoxyamino(ethylidene]-5,5-                                                                   n.sub.D.sup.18.5 1.5088                                 dimethylcyclohexane-1,3-dione                                          21      2-[1-(ethoxyamino)propylidene]-                                                                       n.sub.D.sup.24.5 1.5188                                 cyclohexane-1,3-dione                                                  22      2-[1-(ethoxyamino)propylidene]-5-                                                                     m.p. 65-66° C                                    (4-methylphenyl)cyclohexane-1,3-dione                                  23      2-[1-(ethoxyamino)propylidene]-5-(3-                                                                  m.p. 44-45° C                                    chlorophenyl)cyclohexane-1,3-dione                                     24      2-[1-(ethoxyamino)propylidene]-5-(4-                                                                  m.p. 59-60° C                                    methoxyphenyl)cyclohexane-1,3-dione                                    25      2-[1-(ethoxyamino)propylidene]-5-(4-                                                                  m.p. 92-93° C                                    chlorophenyl)cyclohexane-1,3-dione                                     26      2-[1-(ethoxyamino)propylidene]-5-                                                                     m.p. 67-68° C                                    phenylcyclohexane-1,3-dione                                            27      2-[1-(ethoxyamino)propylidene]-5-                                                                     m.p. 92-96° C                                    styrylcyclohexane-1,3-dione                                            28      2-[1-(ethoxyamino)propylidene]-5-(2-                                                                  m.p. 50-52° C                                    furyl)cyclohexane-1,3-dione                                            29      2-[1-(ethoxyamino)propylidene]-5-(2-                                                                  m.p. 68-69° C                                    thienyl)cyclohexane-1,3-dione                                          30      2-[1-(ethoxyamino)propylidene]-5-                                                                     n.sub.D.sup.20 1.5045                                   methylcyclohexane-1,3-dione                                            31      2-[1-(ethoxyamino)propylidene]-5,5-                                                                   n.sub.D.sup.24 1.5027                                   dimethylcyclohexane-1,3-dione                                          32      2-[1-(ethoxyamino)propylidene]-5-iso-                                                                 n.sub.D.sup.18 1.5111                                   propylcyclohexane-1,3-dione                                            33      2-[1-(ethoxyamino)propylidene]-5-                                                                     n.sub.D.sup. 18.5 1.5019                                hexylcyclohexane-1,3-dione                                             34      2-[1-(ethoxyamino)propylidene]-4-                                                                     n.sub.D.sup.21 1.5081                                   methyl-5,5-dimethylcyclohexane-1,3-                                            dione                                                                  35      2-[1-(ethoxyamino)propylidene]-4,4-                                                                   n.sub.D.sup.18 1.4946                                   dimethylcyclohexane-1,3-dione                                          36      2-[1-(ethoxyamino)propylidene]-4-                                                                     m.p. 47-48° C                                    cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                  37      2-[1-(ethoxyamino)propylidene]-4-                                                                     n.sub.D.sup.24 1.5070                                   methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                       38      2-[1-(ethoxyamino)propylidene]-4-                                                                     n.sub.D.sup.18 1.5040                                   ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                       39      2-[1-(ethoxyamino)propylidene]-4-n-                                                                   n.sub.D.sup.25 1.5078                                   propylcyclohexane-1,3-dione                                            40      2-[1-(ethoxyamino)propylidene]-4-iso-                                                                 n.sub.D.sup.21 1.5055                                   butylcyclohexane-1,3-dione                                             41      2-[1-(methoxymethoxyamino)propylidene]-                                                               n.sub.D.sup.27 1.5017                                   5,5-dimethylcyclohexane-1,3-dione                                      42      2-[1-(buthoxymethoxyamino)propyli-                                                                    n.sub.D.sup.27 1.4927                                   dene]-5,5-dimethylcyclohexane-1,3-                                             dione                                                                  43      2-[1-(methylthioethoxyamino)propyli-                                                                  n.sub.D.sup.27 1.5582                                   dene]-5,5-dimethylcyclohexane-1,3-                                             dione                                                                  44      2-[1-(methylthioethoxyamino)propyli-                                                                  n.sub.D.sup.27 1.5328                                   dene]-5-isopropylcyclohexane-1,3-dione                                 45      2-[1-(methoxyethoxyamino)propylidene]-                                                                n.sub.D.sup.20 1.5100                                   5,5-dimethylcyclohexane-1,3-dione                                      46      2-[1-(ethoxycarbonylmethoxyamino)pro-                                                                 n.sub.D.sup.20 1.5019                                   pylidene]-4,4-dimethylcyclohexane-1,3-                                         dione                                                                  47      2-[1-(propoxyamino)propylidene]-5,5-                                                                  n.sub.D.sup.26 1.4994                                   dimethylcyclohexane-1,3-dione                                          48      2-[1-(allyloxyamino)propylidene]-                                                                     n.sub.D.sup.25 1.5265                                   cyclohexane-1,3-dione                                                  49      2-[1-(allyloxyamino)propylidene]-5-                                                                   n.sub.D.sup.20.5 1.5200                                 methylcyclohexane-1,3-dione                                            50      2-[1-(allyloxyamino)propylidene]-5,5-                                                                 n.sub.D.sup.24 1.5119                                   dimethylcyclohexane-1,3-dione                                          51      2-[1-(allyloxyamino)propylidene]-5-                                                                   n.sub.D.sup.23.5 1.5140                                 isopropylcyclohexane-1,3-dione                                         52      2-[1-(allyloxyamino)propylidene]-5-                                                                   n.sub.D.sup.18.5 1.5082                                 hexylcyclohexane-1,3-dione                                             53      2-[1-(allyloxyamino)propylidene]-5-                                                                   n.sub.D.sup.22 1.5452                                   (2-furyl)cyclohexane-1,3-dione                                         54      2-[1-(allyloxyamino)propylidene]  -5-                                                                 m.p. 48-50° C                                    phenylcyclohexane-1,3-dione                                            55      2-[1-(allyloxyamino)propylidene]-5-                                                                   n.sub.D.sup.21 1.5851                                   styrylcyclohexane-1,3-dione                                            56      2-[1-(allyloxyamino)propylidene]-4-                                                                   n.sub.D.sup.27 1.5338                                   bromo-6,6-dimethylcyclohexane-1,3-                                             dione                                                                  57      2-[1-(allyloxyamino)propylidene]-4-                                                                   n.sub.D.sup.26 1.5365                                   bromo-5,5-dimethylcyclohexane-1,3-                                             dione                                                                  58      2-[1-(allyloxyamino)propylidene]-4-                                                                   m.p. 62-63° C                                    cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                  59      2-[1-(allyloxyamino)propylidene]-4-                                                                   n.sub.D.sup.24.5 1.5088                                 methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                       60      2-[1-(allyloxyamino)propylidene]-4-                                                                   n.sub.D.sup.20 1.5146                                   ethoxycarbonyl-5-methylcyclohexane-                                            1,3-dione                                                              61      2-[1-(allyloxyamino)propylidene]-4-                                                                   n.sub.D.sup.18 1.5079                                   ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                       62      2-[1-(allyloxyamino)propylidene]-4-                                                                   n.sub.D.sup.22 1.5078                                   ethoxycarbonyl-4-echycyclohexane-1,3-dione                             63      2-[1-(allyloxyamino)propylidene]-4-                                                                   n.sub.D.sup.21 1.5138                                   methyl-5,5-dimethylcyclohexane-1,3-                                            dione                                                                  64      2-[1-(allyloxyamino)propylidene]-4,4-                                                                 n.sub.D.sup.18 1.5138                                   dimethylcyclohexane-1,3-dione                                          65      2-[1-(allyloxyamino)propylidene]-4-                                                                   n.sub.D.sup.20 1.5152                                   isopropylcyclohexane-1,3-dione                                         66      2-[1-(allyloxyamino)propylidene]-4-n-                                                                 n.sub.D.sup.25 1.5103                                   propylcyclohexane-1,3-dione                                            67      2-[1-(allyloxyamino)propylidene]-4-n-                                                                 n.sub.D.sup.21.5 1.5134                                 butylcyclohexane-1,3-dione                                             68      2-[1-(allyloxyamino)propylidene]-4-                                                                   n.sub.D.sup.25 1.5091                                   n-pentylcyclohexane-1,3-dione                                          69      2-[1-(propargyloxyamino)propylidene]-                                                                 n.sub.D.sup.18.5 1.5218                                 5,5-dimethylcyclohexane-1,3-dione                                      70      2-[1-(methallyloxyamino)propylidene]-                                                                 n.sub.D.sup.23 1.5107                                   5,5-dimethylcyclohexane-1,3-dione                                      71      2-[1-(n-butoxyamino)propylidene]-5,5-                                                                 n.sub.D.sup.18.5 1.5027                                 dimethylcyclohexane-1,3-dione                                          72      2-[1-(isobutoxyamino)propylidene]  -                                                                  n.sub.D.sup.23 1.4976                                   5,5-dimethylcyclohexane-1,3-dione                                      73      2-[1-(benzyloxyamino)propylidene]-5,5-                                                                m.p. 58-59° C                                    dimethylcyclohexane-1,3-dione                                          74      2-[1-(methoxyamino)butylidene]-5,5-                                                                   n.sub.D.sup.23 1.4940                                   dimethylcyclohexane-1,3-dione                                          75      2-[1-(ethoxyamino)butylidene]-5,5-                                                                    n.sub.D.sup.21 1.4965                                   dimethylcyclohexane-1,3-dione                                          76      2-[1-(ethoxyamino)butylidene]-5-                                                                      n.sub.D.sup.18 1.5068                                   isopropylcyclohexane-1,3-dione                                         77      2-[1-(ethoxyamino)butylidene]-5-                                                                      n.sub.D.sup.18.5 1.5005                                 hexylcyclohexane-1,3-dione                                             78      2-[1-(ethoxyamino)butylidene]-4-                                                                      m.p. 83-87° C                                    cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                  79      2-[1-(ethoxyamino)butylidene]-4-                                                                      n.sub.D.sup.24.5 1.5007                                 methoxycarbonyl-5,5-dimethyl-                                                  cyclohexane-1,3-dione                                                  80      2-[1-(ethoxyamino)butylidene]-4-                                                                      n.sub.D.sup.21.5 1.4990                                 ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                       81      2-[1-(ethoxyamino)butylidene]-4,4-                                                                    n.sub.D.sup.20 1.5050                                   dimethylcyclohexane-1,3-dione                                          82      2-[1-(isopropoxyamino)butylidene]-                                                                    n.sub.D.sup.31 1.4939                                   5,5-dimethylcyclohexane-1,3-dione                                      83      2-[1-(allyloxyamino)butylidene]-5,5-                                                                  n.sub.D.sup.21 1.5089                                   dimethylcyclohexane-1,3-dione                                          84      2-[1-(allyloxyamino)butylidene]-5-                                                                    n.sub.D.sup.18 1.5135                                   isopropylcyclohexane-1,3-dione                                         85      2-[1-(allyloxyamino)butylidene]-5-                                                                    n.sub.D.sup.18.5 1.5051                                 hexylcyclohexane-1,3-dione                                             86      2-[1-(allyloxyamino)butylidene]-5-                                                                    m.p. 52-53° C                                    (4-methoxyphenyl)cyclohexane-1,3-dione                                 87      2-[1-(allyloxyamino)butylidene]-5-                                                                    n.sub.D.sup.25.5 1.5657                                 (3-chlorophenyl)cyclohexane-1,3-dione                                  88      2-[1-(allyloxyamino)butylidene]-5-                                                                    m.p. 36-37° C                                    (4-chlorophenyl)cyclohexane-1,3-dione                                  89      2-[1-(allyloxyamino(butylidene]-4-                                                                    m.p. 105-108° C                                  cyano-5,5-dimethylcyclohexane-1,3-                                             dione                                                                  90      2-[1-(allyloxyamino)butylidene]-4-                                                                    n.sub.D.sup.24.5 1.5063                                 methoxycarbonyl-5,5-dimethylcyclo-                                             hexane-1,3-dione                                                       91      2-[1-(allyloxyamino)butylidene]-4-                                                                    n.sub.D.sup.21 1.5066                                   ethoxycarbonyl-5,5-dimethylcyclo-                                              hexane-1,3-dione                                                       92      2-[1-(allyloxyamino)butylidene]-4-                                                                    n.sub.D.sup.22.5 1.5078                                 ethoxycarbonyl-4-ethylcyclohexane-                                             1,3-dione                                                              93      2-[1-(allyloxyamino)butylidene]-4,4-                                                                  n.sub.D.sup.18 1.4753                                   dimethylcyclohexane-1,3-dione                                          94      2-[1-(allyloxyamino)butylidene]-4-                                                                    n.sub.D.sup.23.5 1.5058                                 isopropylcyclohexane-1,3-dione                                         95      2-[1-(propargyloxyamino)butylidene]-                                                                  n.sub.D.sup.31 1.5132                                   5,5-dimethylcyclohexane-1,3-dione                                      96      2-[1-(hexyloxyamino)butylidene]-5,5-                                                                  n.sub.D.sup.25 1.4725                                   dimethylcyclohexane-1,3-dione                                          97      2-[1-(ethoxyamino)isobutylidene]-                                                                     n.sub.D.sup.23 1.5013                                   5,5-dimethylcyclohexane-1,3-dione                                      98      2-[1-(ethoxyamino)hexylidene]-5,5-                                                                    n.sub.D.sup.31 1.4881                                   dimethylcyclohexane-1,3-dione                                          99      2-[1-(allyloxyamino)hexylidene]-5,5-                                                                  n.sub.D.sup.31 1.5040                                   dimethylcyclohexane-1,3-dione                                          100     2-[1-(ethoxyamino)benzylidene]-5,5-                                                                   m.p. 150-151° C                                  dimethylcyclohexane-1,3-dione                                          101     2-[1-(allyloxyamino)benzylidene]-5,5-                                                                 m.p. 169-170° C                                  dimethylcyclohexane-1,3-dione                                          102     2-[1-(ethoxyamino)propylidene]-5,5-                                                                   n.sub.D.sup.21 1.5272                                   pentamethylenecyclohexane-1,3-dione                                    103     2-[1-(allyloxyamino)propylidene]-5,5-                                                                 n.sub.D.sup.21 1.5336                                   pentamethylenecyclohexane-1,3-dione                                    104     2-[1-(ethoxyamino)propylidene]-4,5-                                                                   n.sub.D.sup.21 1.5282                                   tetramethylenecyclohexane-1,3-dione                                    105     2-[1-(allyloxyamino)propylidene]-4,5-                                                                 n.sub.D.sup.21 1.5347                                   tetramethylenecyclohexane-1,3-dione                                    106     Sodium salt of 2-[1-(ethoxyamino)-                                                                    m.p. 225-226° C(d.)                              ethylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                              107     Potassium salt of 2-[1-(ethoxyamino)-                                                                 m.p. 110-112° C(d.)                              ethylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                              108     Copper salt of 2-[1-(ethoxyamino-                                                                     m.p. 156-157° C(d.)                              ethylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                              109     Copper salt of 2-[1-(ethoxyamino)-                                                                    m.p. 161-164° C(d.)                              ethylidene]-4-cyano-5,5-dimethylcyclo-                                         hexane-1,3-dione                                                       110     Sodium salt of 2-[1-(ethoxyamono)-                                                                    m.p. 110-120° C(d.)                              ethylidene]-4-methoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                          111     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.164-165° C(d.)                               ethylidene]- 5-ethylcyclohexane-1,3-                                           dione                                                                  112     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.188-189° C(d.)                               ethylidene]-5-phenylcyclohexane-1,3-                                           dione                                                                  113     Copper salt of 2-[1-(allyloxyamino)                                                                   m.p.154-158° C(d.)                               ethylidene]-4-cyano-5,5-dimethylcyclo-                                         hexane-1,3-dione                                                       114     Sodium salt of 2-[1-(allyloxyamino)-                                                                  m.p.193-194° C(d.)                               ethylidene]-4-methoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                          115     Sodium salt of 2-[1-(allyloxyamino)-                                                                  m.p.110-120° C(d.)                               ethylidene]-4-ethoxycarbonyl-5,5-                                              dimethylcyclohexane-1,3-dione                                          116     Copper salt of 2-[1-(methylthio-                                                                      m.p. 110° C(d.)                                  methoxyamino) ropylidene]-5,5-                                                 dimethylcyclohexane-1,3-dione                                          117     Copper salt of 2-[1-(ethoxyamino)-                                                                    m.p.197-198° C(d.)                               propylidene]-5-(2-furyl)cyclohexane-                                           1,3-dione                                                              118     Copper salt of 2-[1-(ethoxyamino)-                                                                    m.p.184-185° C(d.)                               propylidene]-5-(2-thienyl)cyclohexane-                                         1,3-dione                                                              119     Copper salt of 2-[1-(ethoxyamino)-                                                                    m.p. 186-188° C(d.)                              propylidene]-5-(4-chlorophenyl)-                                               cyclohexane-1,3-dione                                                  120     Copper salt of 2-[1-(ethoxyamino)-                                                                    m.p.184-185° C(d.)                               propylidene]-5-(3-chlorophenyl)-                                               cyclohexane-1,3-dione                                                  121     Copper salt of 2-[1-(ethoxyamino)-                                                                    m.p. 183- 184° C(d.)                             propylidene]-5-(4-methylphenyl)-                                               cyclohexane-1,3-dione                                                  122     Copper salt of 2-[1-(ethoxyamino)-                                                                    m.p. 81-83° C(d.)                                propylidene]-4-cyano-5,5-dimethyl-                                             cyclohexane-1,3-dione                                                  123     Sodium salt of 2-[1-(ethoxyamino)-                                                                    m.p.188-190° C(d.)                               propylidene]-4-ethoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                          124     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.146-147° C(d.)                               propylidene]-cyclohexane-1,3-dione                                     125     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.129-130° C(d.)                               propylidene]-5-methylcyclohexane-                                              1,3-dione                                                              126     Nickel salt of 2-[1-(allyloxyamino)-                                                                  m.p.169-170° C(d.)                               propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                              127     Calcium salt of 2[1-(allyloxyamino)-                                                                  m.p.107-108° C(d.)                               propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                              128     Cobalt salt of 2-[1-(allyloxyamino)-                                                                  m.p.151-152° C(d.)                               propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                              129     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.145-146° C(d.)                               propylidene]-5-isopropylcyclohexane-                                           1,3-dione                                                              130     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p. 78-80° C(d.)                                propylidene-4-cyano-5,5-dimethyl-                                              cyclohexane-1,3-dione                                                  131     Sodium salt of 2-[1-(allyloxyamino)-                                                                  m.p.175-178° C(d.)                               propylidene]-4-methoxycarbonyl-5,5-                                            dimethylcyclohexane-1,3-dione                                          132     Sodium salt of 2-[1-(allyloxyamino)-                                                                  m.p.110-120° C(d.)                               propylidene]-4-ethoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                          133     Calcium salt of 2-[1-(allyloxyamino)-                                                                 m.p.150-152° C(d.)                               propylidene]-4-propylcyclohexane-                                              1,3-dione                                                              134     Copper salt of 2-[1-(proparglyoxy-                                                                    m.p.126-127° C(d.)                               amino)propylidene]-5,5-dimethylcyclo-                                          hexane-1,3-dione                                                       135     Barium salt of 2-[1-(propoxyamino)-                                                                   m.p.75-78° C(d.)                                 propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                              136     Calcium salt of 2-[1-(isobutoxyamino)-                                                                m.p.195-200° C(d.)                               propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                              137     Copper salt of 2-[1-(butoxyamino)-                                                                    m.p.123-125° C(d.)                               propylidene]-5,5-dimethylcyclohexane-                                          1,3-dione                                                              138     Calcium salt of 2-[1-(ethoxyamino)-                                                                   m.p.180° C(d.)                                   butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                              139     Copper salt of 2-[1-(ethoxyamino)-                                                                    m.p.98-101° C(d.)                                                       - butylidene]-4-cyano-5,5-dimethyl-                     cyclohexane-1,3-dione                                                  140     Sodium salt of 2-[1-(ethoxyamino)-                                                                    m.p.183-185° C(d.)                               butylidene]-4-methoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                          141     Nickel salt of 2-[1-(allyloxyamino)-                                                                  >m.p.250° C(d.)                                  butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                              142     Cobalt salt of 2-[1-(allyloxyamino)-                                                                  m.p.153-154° C(d.)                               butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                              143     Sodium salt of 2-[1-(allyloxyamino)-                                                                  m.p.80-82° C                                     butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                              144     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.145-146° C(d.)                               butylidene]-5-isopropylcyclohexane-                                            1,3-dione                                                              145     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.105-106° C(d.)                               butylidene]-5-hexcylcyclohexane-1,3-                                           dione                                                                  146     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.182-183° C(d.)                               butylidene] -5-(4-methoxyphenyl)cyclo-                                         hexane-1,3-dione                                                       147     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.92-95° C(d.)                                 butylidene]-4-cyano-5,5-dimethyl-                                              cyclohexane-1,3-dione                                                  148     Sodium salt of 2-[1-(allyloxyamino)-                                                                  m.p.192° C(d.)                                   butylidene]-4-methoxycarbonyl-5,5-                                             dimethylcyclohexane-1,3-dione                                          149     Sodium salt of 2-[1-(allyloxyamino)-                                                                  m.p.110-120° C(d.)                               butylidene]-4-ethoxycarbonyl-5,5-                                              dimethylcyclohexane-1,3-dione                                          150     Copper salt of 2-[1-(benzyloxyamino)-                                                                 m.p.126-127° C(d.)                               butylidene]-5,5-dimethylcyclohexane-                                           1,3-dione                                                              151     Copper salt of 2-[1-(allyloxyamino)-                                                                  m.p.178-179° C(d.)                               propylidene]-4,5-tetramethylenecyclo-                                          hexane-1,3-dione                                                       152     2-[1-(allyloxyamino)butylidene]-5,5-                                                                  m.p.47-49° C                                     dimethylcyclohexane-1,3-dione hydrate                                  153     2-[1-(allyloxyamino)propylidene]-5,5-                                                                 m.p.52-54° C                                     dimethylcyclohexane-1,3-dione hydrate                                  154     2-[1-(allyloxyamino)propylidene]-5-                                                                   m.p.46-48° C                                     methylcylohexane-1,3-dione hydrate                                     155     2-[1-(allyloxyamino)propylidene]-5-                                                                   m.p.48-50° C                                     phenylcyclohexane-1,3-dione hydrate                                    156     2-[1-(ethoxyamino)propylidene]-5-                                                                     m.p.67-68° C                                     phenylcyclohexane-1,3-dione hydrate                                    157     2-[1-(allyloxyamino)propylidene]-5,5-                                          diethylcyclohexane-1,3-dione                                           __________________________________________________________________________      m.p.: melting point                                                            n.sub.D : refractive index                                                     d. : decomposition                                                       

Hereinafter, the compounds of this invention are represented by Compound No. in Table 1.

As mentioned previously, it has been found that the compounds of the invention possess superior herbicidal activity. The paragraphs which follow described in more detail the utility of this invention.

The compounds of the invention are particularly effective in the control of grass weeds such as annual bluegrass (Poa annua), water foxtail (Alopecurus aequalis), large crabgrass (Digitaria adscendens), green foxtail (Panicum viride L), wild oat (Avena fatua L) etc. and they hardly injure broad leaf crops such as adzuki bean (Phaseolus angularis) and soy bean (Glycine max) and sugar beets which easily suffer phyto-toxicity. Namely, the compounds of the invention are the selective herbicide.

It is already known that 4-hydroxy-6-methyl-α-pyrone derivatives has herbicidal properties as shown in Japanese Patent Publication No. 16916/1971.

But in order to destory completely the said grass weeds, a large amount of the above herbicidal chemical is required and this is one drawback for above mentioned herbicidal compound.

In the other words, according to the descriptions of above mentioned prior art and the results of the later additional experiments by the inventors, a chemical amount containing 500g of effective ingredient, in proportion to 10 are ("are" is 100 square meters) of area is able to give an expected effect in the case of employing it practically, but another chemical amount containing 250g of effective ingredient, in proportion to 10 are of area is not able to wither grass weeds to death, in the other words, it cannot give a perfect herbicidal effect.

But, in the event of employing the compound of the present invention as a herbicide, a chemical amount containing 250g of effective component, as a matter of course, further a chemical amount containing 125g of less of effective ingredient, in proportion to 10 are of area, in compliance with the same treating method of conventional herbicide indicates a strong herbicidal effect and thereby a perfect prevention and extermination of weeds can be expected.

In case of foliar treatment using the compounds of the present invention, even the same amount of chemical which makes barnyard grass of grass weeds completely kill gives no damages to broadleaf plants such as radish, soy bean (Glycine max), garden pea (Pisum sativum), spinach (Spinacia oleracea) sugar beets and carrot at all, and in case of soil treatment before germination, even the same amount of chemicals which prevents large crab-grass (Digitaria adscendens) germinating gives no damages to seeds of broad leaf plants at all.

As mentioned above, a secure safety to the broadleaf crop against phytotoxicity of the herbicide is extremely high and as to its application, in the other weeds, its applicable time, its applying location and its applying concentration, it has a very broad extent and it can be used in the wider extent.

It is another advantage of the present invention that a residual toxicity in the soil or the plant and an acute toxicity for warm blooded animals and fishes are not feared because the said compounds can be employed with a low chemical concentration.

The compounds of this invention can be applied directly to the soil as pre-emergence treatment or as post-emergence treatment to plant foliage, or they can be mixed intimately with the soil, preferably post-emergence treatment to plant foliage, and may be applied to soil or plant foliar at rates of 50-1000g per 10 are, preferably 50-200g per 10 are, more preferably about 100g per 10 are.

The method of the present invention comprehends the empolyment of a liquid or solid composition containing one or more of the present compounds as an active ingredient.

The active ingredient of this invention may be formulated by mixing with suitable carriers in a form generally used in agricultural chemicals such as wettable powder, emulsifiable concentrate, dust formulation, granular formulation, water soluble powder and aerosol. As solid carriers, bentonite, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vermiculite, clay and others are used. As liquid carriers, kerosene, mineral oil, petroleum, solvent naphtha, benzene, xylene, cyclohexane, cyclohexanone, dimethylformamide, alcohol, acetone, and others are used. Sometimes surface active agent is added in order to give a homogeneous and stable formulation.

The compounds of this invention also can be applied admixed with other chemicals which are used in agronomic and horticultural management and are compatible with the compounds of this invention. Such chemicals can be, but are not restricted to, the classes of chemicals commonly known as plant nutrients, fertilizers, insecticides, acaricides, fungicides, herbicides and nematocides.

As for known herbicide it is recommended that the compound of the present invention is applied admixed with urea derivatives such as 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea, or N-(3,4-dichlorophenyl)N',N'-dimethylurea, triazine dervatives such as 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, or 2-chloro-4,6-bis(ethylamino)-s-triazine and amide derivatives such as N-1-naphthyl-phthalamic acid.

The concentrations of the active ingredients in the herbicidal composition of this invention vary according to type of formulation, and they are, for example, used in a range of 5 - 80 weight percent, preferably 10 - 60 weight percent, in wettable powder, 5 - 70 weight percent, preferably 20 - 60 weight percent, in emulsifiable concentrates, and 0.5 - 30 weight percent, preferably 1 - 10 weight percent in dust formulation.

Thus, a wettable powder or an emulsifiable concentrate produced thereto is diluted with water to a specified concentration and thereby, it is used as a liquid suspension or a liquid emulsion for treating soils or plant foliars. Further, a dust formulation is directly used for the soil treatment or the foliar treatment.

The non-limiting examples for the herbicidal composition is illustrated as follows:

Example 10. Wettable Powder

    ______________________________________                                                          Parts by weight                                               ______________________________________                                         Compound 1        20                                                           Diatomaceous earth                                                                               37                                                           Sodium alkylsulfate                                                                               6                                                           Talc              37                                                           ______________________________________                                    

These are mixed homogeneously and reduced to fine particles. Consequently, wettable powder containing 20% of active ingredient is obtained. In practical use, it is diluted to a certain concentration with water and is sprayed as a suspension.

Example 11. Emulsifiable Concentrate

    ______________________________________                                                           Parts by weight                                              ______________________________________                                         Compound 2          40                                                         Xylene              35                                                         Dimethylformamide   15                                                         Polyoxyethylene phenylether                                                                        10                                                         ______________________________________                                    

These are mixed and dissolved.

Consequently, emulsifiable concentrate containing 40% of the active ingredient is obtained. In practical use, it is diluted to certain concentration with water and then is sprayed as an emulsion.

Example 12. Dust Formulation

    ______________________________________                                                         Parts by weight                                                ______________________________________                                         Compound 3         7                                                           Talc              38                                                           Bentonite         10                                                           Clay              38                                                           Sodium alkylsulfate                                                                               7                                                           ______________________________________                                    

These are mixed homogeneously and reduced to fine particles. Fine particles is made into granules having the diameter in the range of 0.5 - 1.0mm by granulator.

Consequently, dust formulation containing 7% of the active ingredient is obtained. In practical use it is directly applied.

The superior herbicidal effect of the novel compounds of this invention is clearly illustrated by the following tests.

Test 1. Pre-emergence (soil treatment)

About 60 seeds of barnyard grass were planted in a pot having 60 square centimeters and coverd slightly with soil. Said pot was kept stagnation state so as to get wet with water

10ml of an aqueous suspension prepared by diluting an emulsifiable concentrate with water to a specified concentration was sprayed on the pot. Two weeks after spraying, the degrees of damage to the plant were observed and estimated by the value of 0 - 5 which have the following meanings:

0: no effect

1: a few slightly burnt spots

2: marked damage to leaves

3: some leaves and parts of stalks partially dead

4: plant partially destroyed

5: plant completely destroyed or no germination The results were shown in Table 2.

                  Table 2                                                          ______________________________________                                                            Application                                                                    rate (g/10 are)                                             Test compound No.    120    60    30  15  7.5                                  ______________________________________                                          31                  --     --    5   4   3                                     50                  --     --    5   5   5                                    107                  --     --    5   2   1                                    108                  --     --    5   3   2                                    126                  --     --    5   3   1                                    127                  --     --    5   3   2                                    128                  --     --    5   5   3                                    137                  --     --    5   3   2                                    141                  --     --    5   5   2                                    142                  --     --    5   5   3                                    143                  --     --    5   5   5                                    152                  --     --    5   4   3                                    155                  --     --    5   5   5                                    Comparative compound                                                            ##STR7##            4      2     0   0   0                                    Untreated                         0                                            ______________________________________                                    

Test 2. Post-emergence (foliar treatment)

About 50 seeds of barnyard grass were planted in a pot having 60 squre centimeters and covered slightly with soil. Said pot was filled with water when the plant was grown to first leaf-stage.

An aqueous suspension prepared by diluting an emulsifiable conentrate with water to a specified conentration was sprayed on the pot. Two weeks after spraying, the degrees of damage to the test plant was observed and estimated by the value of 0 - 5 which have the same meanings as those of Test 1.

The results were shown in Table 3.

                  Table 3                                                          ______________________________________                                                            Application                                                                    rate (g/10 are)                                             Test compound No.    125     62.5    31.3                                      ______________________________________                                          10                  5       4       3                                          18                  5       5       4                                          31                  5       5       4                                          50                  5       5       4                                         107                  5       5       4                                         108                  5       5       3                                         112                  5       4       1                                         124                  5       3       1                                         126                  5       4       3                                         127                  5       4       3                                         128                  5       4       4                                         135                  5       3       1                                         137                  5       5       4                                         141                  5       5       4                                         142                  5       5       5                                         143                  5       5       5                                         150                  5       4       3                                         152                  5       5       5                                         154                  5       4       3                                         155                  5       5       4                                         156                  5       5       4                                         Comparative compound                                                            ##STR8##            4       1       0                                          ##STR9##            3       0       0                                         Untreated                    0                                                 ______________________________________                                    

Test 3. Pre-emergence

Seeds of large carb-grass was planted in a pot having 100 square centimeters. An aqueous suspension prepared by diluting an emulsifiable concentrate with water to a specified concentration was sprayed on the surface of the soil before emergence. 21 days after spraying, the degrees of damage to the test plant was observed and estimated by the value of 0 - 5 which have the same meanings as those of Test 1.

The results were shown in Table 4

                  Table 4                                                          ______________________________________                                                            Application                                                                    rate (g/10 are)                                             Test compound No.    300    120    60  30  15                                  ______________________________________                                          31                  --     5      5   5   4                                    50                  --     5      5   5   5                                    75                  --     5      5   5   5                                    83                  --     5      5   5   5                                    96                  --     5      5   5   4                                   107                  --     5      4   2   --                                  111                  --     5      4   1   --                                  126                  --     5      3   1   --                                  127                  --     5      4   2   --                                  128                  --     5      4   2   --                                  134                  --     5      3   1   --                                  137                  --     5      2   0   --                                  142                  --     5      5   4   --                                  143                  --     5      4   4   --                                  152                  --     5      5   5   4                                   154                  --     5      5   4   3                                   155                  --     5      5   4   4                                   156                  --     5      5   4   4                                   Comparative compound                                                            ##STR10##           4      0      0   0   0                                   Untreated                          0                                           ______________________________________                                    

Test 4. Post-emergence (foliar treatment)

Seeds of large crab-grass was planted in a pot having 100 square centimeters. An aqueous suspension prepared by diluting an emulsifiable concentrate with water to specified concentration was sprayed on the foliar of the test plant at a rate of 100 liter per 10 are.

21 days after spraying, the degrees of damage to the test plant was observed and estimated by the value of 0 - 5 which have the same meanings as those of Test 1. The results were shown in Table 5.

                  Table 5                                                          ______________________________________                                                              Application                                                                    rate (g/10 are)                                           Test compound No.      100    50     25                                        ______________________________________                                          10                    5      5      5                                          18                    5      5      5                                          31                    5      5      4                                          50                    5      5      5                                          75                    5      5      4                                          83                    5      5      5                                         106                    5      3      2                                         108                    5      5      4                                         125                    5      4      4                                         126                    5      5      4                                         127                    5      5      4                                         128                    5      5      4                                         134                    5      4      3                                         135                    5      4      3                                         137                    5      4      2                                         141                    5      5      4                                         142                    5      5      4                                         143                    5      5      5                                         145                    5      3      2                                         152                    5      5      5                                         154                    5      4      4                                         155                    5      5      5                                         156                    5      5      4                                         Comparative compound                                                            ##STR11##             3      2      0                                          ##STR12##             3      1      0                                         Untreated                     0                                                ______________________________________                                     

What is claimed is:
 1. A compound of the formula ##STR13## wherein R₁ is selected from the group consisting of ethyl and propyl.R₂ is selected from the group consisting of ethyl and allyl.
 2. A compound according to claim 1, in which R₁ is propyl, R₂ is allyl.
 3. The sodium, potassium, barium and calcium salts of a compound of the formula ##STR14## wherein R₁ is selected from the group consisting of ethyl and propyl,R₂ is selected from the group consisting of ethyl and allyl.
 4. The sodium salt compound according to claim 3 in which R₁ is propyl, R₂ is allyl. 